Low temperature copolymerization of diolefins, olefins, and aromatic compounds



Patented Apr. 27, 1954 LOW TEMPERATURE COPOLYMERIZATION OF DIOLEFINS, OLEFINS, AND AROMATIC COMPOUNDS George E. Serniuk, Roselle, and John D Ga-rber,

Cranford, N. 1., assignors to Standard Oil De velopment Company, a corporationof Delaware No Drawing. Applioation D'ecember'2; 1949,

Serial No. 130,848

15. Claims. (Cl. 260 -2317) This invention relates to. the manufacture of polymerization products from unsaturated organic materials. More particularly, the present invention relates to a process of preparing resinous masses and to the resins obtainable by said process. I

The reaction of conjugateddienes, olefins and aromatic hydrocarbons toformresinous bodies has been knownforsom time. See; for example, U S;. Patent No; 1,982,707 and No. 2;023,495- to- Gharles A. Thomas; According to the: method disclosed in these'reference's, theresins areipne pared by the application ofisolid aluminum chlo.-' ride or other solid" acid-acting halide. catalyst to; the hydrocarbon mixture attemperatures oil- 209 C; or above; However; the product: isdisclosed: as:' containing a substantial amount of. insoluble material. It has now been found that essentially gel free' (i1 e. free'frominsoluble material). resinous poly;- mersof varying softening point: and. degree of. unsaturation can be preparedsin; high. yields? at: fairly high catalyst efficiencies from diolefins, open-chain olefins and aromatic compounds free from olefinic unsaturation by effecting the reaction at temperatures below C. using a dissolved Friedel-Crafts type catalyst.

Suitable diolefins include butadiene, isoprene, piperylene, dimethylbutadiene, myrcene, dijmethallyl, cyclopentadiene, terpenes, etc. Mono-v olefins include ethylene, propylene, butane-I, butene-z, isobutylene, amylenes, etc. matic component includes benzene, toluene, xylene,.-mesitylene,, naphthalene, methyl. naph=-; thalene; antl' racene, phenanthrene hydrindene, tetraliin. cyclohexylbenzene and. their. alkyl, aryl, cycloalkyLaralkyl; halogen, alkoxy and nitro derivatives such. as. chiorobenzene, fluorobenzene, halogenated toluene, anisole, phenetole, dimethoxy benzene. halogenated naphthalene; methoxy naphthalene,v dimethoxy naphthalene, diphenyl sulfone, diphenyl ether, chlorodiphenyl ether, benzene sulfonyl chloride, benzoyl chloride, etc. I

Diole'fins, such as butadiene; and ol'efiha, Suchas butylenapccur in petroleum distillat'es result ing from high temperature pyrolysis; ran ample, itis possible to produce a four carbon hydrocarbon: fraction by the pyrolysis of Pennsyl vania gas oil at 1400 F. with a contact time of The arm 28 seconds and in the presence of 5 per cent. of"

steam. Under these conditions, a weight yield of four carbon hydrocarbons from the charge stock of 10.1% is obtained. The four carbon hydrocarbonsconsist of 38% butadiene, 38% butylene and 24% unreacted butane. After removal of the-butane, such a" fraction can b mixedwith an aromatic hydrocarbon such as benzene, etc., and polymerized under the conditions describedbelow to produce a resin. However, butadiene may be 2 produced by one of several methods, such as effecting an aldol' condensation of acetaldehyde; hydrogenating the product to a glycol and finally dehydrating the glycol to= LS-butadiene. This diolefincan then be mixed with an olefin, such as amylene, and an aromatic hydrocarbon, such asbenzene'.

Furthermore, diolefins can be produced by dehydrogenation from the corresponding olefin, for" example, butadiene can be produced by the de-l hydrogenation of normal butylene. In such.

cases, it is unnecessary to separate the diolefins.

from the unreacted olefin and the mixture of butadiene and butylene can be employed directly in conjunction with an aromatic hydrocarbon in accordance with this "invention.

According." to the-processof. this invention, the threecomponents, 1. e; the olefin, diolefin and aromatic hydrocarbon. are mixed: and, cooled to; temperatures ranging from 0 C. to l0 or C. to-temperatures as'lovv as 100 C. or -l50 C. The polymerization reaction is then: conducted. by the application of a dissolved, Friedel-Crafts type, catalyst such as aluminum chloride, aluminum bromide, titanium 11811133011101 ride, boron trifluoride, uranium chloride andthe like, dissolved in a low-freezing; inert or non-- complex forming solvent, such as ethyl or methyl;

chloride, or carbon disulfide, orthe like. The catalyst solution preferably contains from 0.1%

t'o 5% of a dissolved active metal halide catalyst and is preferablyused in the ratio of about 10 parts per 100 parts of the diolefin. The polymerization proceeds promptly with the development of a substantial amount of heat and the production of apolymer in solution without the formation of insoluble gel;

The products so obtained are suitable as mm forming agents, varnishes and thelike, andhave superior baked-film properties;

The following examples are given as illustrative of the invention, but it is to be understoodas not liinitative of the scope thereof.

Example? I A mixtureof fiopartsbutadiene, 25 parts diisobutylene. and 25. parts chlorobenzene was diluted oughwater washingthe. dry resin was recovered.

by'ilashing oiT the. naphtha and any unchanged. chlorobenzene. A yield of parts of brittle,

clear resin was obtained which showed an excellent reactivity toward linseed oil and gave'a varnish with superior grease resistance.

Example II A similar experiment. to that described in Ex- 3 ample I was ruri except that a feed of 50 parts butadiene, 25 parts diisobutylene and 25 parts anisole was used. A product was obtained in good yield.

Example III A butadiene-isobutylene-toluene feed containing a 60-20-20 ratio of monomers was diluted with methyl chloride and treated with AlCls ethyl chloride catalyst under reflux. A yield of 64% 4 mg 7.63 g. AlCla/lOO cc. of ethyl chloride was added to the above agitated solution in increments. A total of 125.1 g. of A1C13 was added. The catalyst was then quenched with isopropyl 5 alcohol, the methyl chloride and ethyl chloride was allowed to flash off and the product was then heated to 450 F. to drive off solvents and any remaining phenol not removed by water washing. The final product which was dark in color and fluid amounted to 365 g. This correof soft ioduct, based on total feed, was obtained at a cafialyst efficiency of 74 The bodymg sponds to a 39% yield based on the total feed or time for a gallon linseed oil varnish was 4% 49% based. on the olefins: The ylleld of proquct hours at and the dried and baked could be increased considerably if a sufiicient varnish film properties were found to be superior F 2 of i used to form the dlchloro to those made from a copolymer of butadiene-iso- 0 a'ummum p ena butylene alone prepared in the same manner. Example VI A 5-liter 3-way flask filled with a mechanical oopolymerofButa TripolymerofButastirrer, Dry Ice cooled reflux condenser, therdiene-Isobutylene gfffg g 2O mometer and catalyst delivery funnel was charged Test with the following:

Air-Dried Baked Air-Dried Baked 1,3-b11tadiene 483 Propylene (95%) g 262 Hardness 6 0 0 0 Toluene (Bakers) g- 1 g igf g g g g 8 Methyl chloride 522 giiusliizc Resistance: g g 3 To the above charge was then added AlCla ex 951591106 dissolved in ethyl chloride concentration being s R t 9 0 0 0 We 3.92 g. A1c13 100 cc. of ethyl chlor1de. A total ammmcted. 9=c0mp1etefanum of 300 cc. of catalyst solution was introduced in E m I IV increments over a period of 90 minutes. The 1m 10 e reaction temperature was 27 to -l8 C. At A series of butadiene-isobutylene-benzene polythe end of 9'7 minutes the catalyst was quenched mers Was prepared which indicated that the with isopropyl alcohol. The polymer solution physical characteristics of the polymer varied was diluted with 500 cc. of 54 naphtha. Methyl between a soft, penetrable product to a hard, 5 and ethyl chlorides were allowed to weather of! brittle resin depending upon the ratio of monoat room temperature. The polymer solution was mers in the feed. The results are shown below: freed of catalyst residues by water washing. The

Butadicne in Feed (Parts) 28.7-.. 44.6--- 54.1-.- 40.8 32. Isobutylene in Feed (Pa s 29.8 23.1-.. 18.9 20.5... 16. Benzene lll Feed (Parts) 41.5-.. 32.2-.. 26.4-.. 38.8"-.. 52. Percent yield on 'lotalFeed 56. 55. 54-.. 5s 51. Percent yield on Olefins 9e 7a.-.. 95... 105. Catalyst Efficiency.-. 62 106 175. 38 28. Product State Soft," Soft. Soft. Hard Hard. Softening common 42 58.5 Ge1led 81.5.

Example V solvents were stripped from the polymer by heat- A 5-liter 3-way flask fitted with a mercury sealed mechanical stirrer, Dry Ice cooled reflux condenser, catalyst delivery funnel and thermometer was charged with the following:

414 g. butadiene (vapor passed over CaClz and condensed) 338 g. diisobutylene (close out) 188 g. phenol 552 cc. methyl chloride ing to 450 F. A total of 522 g. of soft, light amber colored polymer was obtained, corresponding to a conversion of 56%. The product had an iodine number of 162.7. In a similar manner polymers were prepared from butadiene-propylene-toluene feed ratios of 43.4/233/333 and 56.6/30A/13 respectively. Polymer yields of 58.5 and 44.6% were obtained for the above feed ratios respectively. The properties of linseed oil varnishes of these polymers are summarized in the followl A solution of AlCls in ethyl chlor1de contam- 6 mg table:

Properties Varnish Preparation, 15 gal. length Varnish Film Properties Poly- Catalyst Rat1o,D1olefin/ mer Olefin/Aromatic 552E322}; Yield, Softening 000k Tune Base Gardner Reduced Percent P oint, Iz# Loss, Cure H W G C F S Hrs. Min. Percent Color Vis.

52/27.9/20.1 1.253 56 Soft.-." 162.7 3 :30 10.6 10-11 L-M 34 g- 8 g (1) 8 g 4 0 43.4/23.3/33.3 2.09 58.5 d0 130.4 3 :45 13.6 16-17 J-K 39 A. 0 1 7 0 0 3 B. 0 0 0 0 0 0 56.6/39A/13 0.633 44.6 "410..." 201.6 1 :38 3.03 8-9 J 40 A 0 6 7 6 0 6 B. 0 0 0 3 0 0 55/45/0- 29 10-11 3-1 A. 1 7 5 9 6 7 B- 0 0 0 6 0 6 Iii-hardness; W-water resistance; G-grease resistance; O-caustic resistance; F-flex; S--soap resistance.

Varnlshes formed by the time temp. reached 560 F.

agedaces A sample of a copolymer of butadiene and acrylonitrile containing 26% acrylonitrile (100 6 certain degree of alteration of the physical properties of the final product. Thus, it may be desirable to relate the concentration of the individual components and their period of polymersaid unsaturated materials; dilution of the reaction mix; etc., without departing from the essence of the invention. Of course, as is evident to one skilled in the art, variations relating to th reactants per se will be accompanied by av p Was p e 011 the 6. m l and a tot 5 i'zation to the rates of polymerization of the 0f Parts Of the P 1 alkvlate des bed in individual substances as a means of controlling Example V was added. A very clear, smooth the composition of the final product. Furthersheet was Obt ed. A Control Sample w Simimore, since the aromatic hydrocarbons and the 131:1? "treated 21110120 Darts buty p th lat iv diolefins polymerize more readily than do the was added. Standard Perbunanc'omp'ounds were 170 l fi s, the ultimate composition of the products made up and cured at 287 F. for 15, 30, 45 d lends itself to'control by this means. Generally, 90 minutes- The tensile-elongation ata as We however, it is desirable to carry out this reaction as p cent swell in SR-G after 48 hours are shown so that substantial amounts of the olefins enter below: into the final polymerization products.

Dibutyl Phthalate Plasticizer Alkylated Phenol Plasticizer Cure glirme Y 5 at Tensile, ggg Swell, I Tensile, gg Swell,

#/Sq.In. Prceilt Percent #ISq. In. Perceht Percent Compound recipe: It is not possible at this time to state the mechy 100 anism of this invention, nor is the invention Carbon Black 45 limited to any theories as to the process of the Zinc oxide 5 reaction,

Stearic acid 1 The nature of the present invention having thus bu yl Dhthalate 15 been described, what is claimed as new and useful ta 1 and desired to be secured by Letters Patent is:

Sulfur 1- We claim;

Diphenyiguanidine 1. A process for the preparation of a resinous It is apparent that the alkylated phenol was polymer which comprises mixing butadiene, isosuperior to the conventional plasticizer in that butylene and toluene in a ratio of 60/20/20, dilutit gave a faster curing stock which showed higher me he mixt r wi h met yl c l ri e, cooling th elongation, higher tensile strength and less exdiluted solution to a temperature between 0 C. traction by an aromatic solvent, and (3., adding thereto 19% by weight based Example VIII 1 on the iced of aluminum chloride catalyst dis- One part of a butadiene-diisobutylene-phenol 83 m ethyl inlonde 5 anc-Oncemmmn Peween 0.1 and 5 A, and separating the resulting resin (obtained as in Example V) and 1.2 parts resin from the rnaciion mixture of alkali refined linseed oil (15 gallon length; 2 A 1 u o process fOl the preparation of a resinous varnish) were heated for 1 hour at 565 F. A 1 mer which comprises mixing 28 7 to 68 of varnish of 18+ Gardner color and :r-6 Gardner 83, 26 0 a n f ene, 16 to 6/0 or an olenn selected from viscosity was obtained. The air dried and baked m a l e group consisting or diisobutylene, isobutylcne, film properties o this varnish are compared with and propylene, and 19 to 52% of an aromatic 9 of varm.sh prepafred butadlene' compound selected from the group consisting of dusobutylene resm and lmseed 5Q chlorobenzene, anisole, toluene, benzene, and phenol, said aromatic compound not being in zgifif ig if gg jgfigf gggfg excess of '52 wt. per cent of the monomeric mix- Linseed Oil Resin-Linseed ture, diluting the mixture with methyl chloride, Test Vamlsh O11 Varmsh cooling the diluted solution to a temperature between 0 C. and -40 C., adding thereto 10% by eg Baked fi Baked weigh based on the feed of an aluminum chloride Film Film Film 71mm catalyst dissolved in ethyl chloride in a concentration between 0.1 and 5%, and separating the Hardness 4 4 s 4 resulting resin from the mixture. g zglgfi g gfif 8 8 8 8 60 3. A process according to claim 2 in which the 1% NaOlEl Resistance 4 4 2 0 olefin 1S isobutylene. ggg g fiz fi t 8 8 g 8 4. A process according to claim 3 in which the aromatic compound is toluene. Rating: 0=unallected1 9=film failure. 5. A process according to claim 2 in which the While in the above examples specific reaction 5 olefin is propylene. conditions are given, the present invention is not 6. A process according to claim 5 in which the limited to such conditions. For example, variaaromatic compound is toluene. tions may be introduced as to the particular 7. A process .according to claim 2 in which the diolefin, olefin and aromatic hydrocarbon conaromatic compound is chlorobenzene. jointly polymerized; the relative proportions of 8. A process according to claim 7 in which the olefin is diisobutylene.

9. A process according to claim 2 in which the diolefin is butadiene.

10. A process according to claim 9 in which the olefin is isobutylene.

11. A process according to claim 10 in which the aromatic compound is benzene.

12. A process according to claim 2 in which the olefin is diisobutylene.

13. A process according to claim 12 in which the aromatic compound is anisole.

14. A composition comprising a copolymer of butadiene, an olefin selected from the group consisting of diisobutylene, isobutylene, and propylone, and an aromatic compound selected from the group consisting of chlorobenzene, anisole, toluene, benzene, and phenol, said aromatic compound not being in excess of 52 wt. per cent of monomeric mixture, said copolymer being dissolved in linseed oil and being prepared by the application at a temperature below C. of aluminum chloride dissolved in ethyl chloride in a concentration between 0.1 and to a feed consisting of between 28.7-61.6% butadiene, 16-36% of olefin and 19-52% of the aromatic.

15. A process for the preparation of a resinous polymer which comprises mixing butadiene, isobutylene and benzene in a ratio of 32/16/52,

diluting the mixture with methyl chloride, cooling the diluted solution to a temperature between 0 C. and C., adding thereto an aluminum chloride catalyst dissolved in methyl chloride in a concentration between 0.1 and 5% and separating the resulting resin from the reaction mixture.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,438,340 Johnson Mar. 23, 1948 2,476,000 Sparks et a1. July 12, 1949 2,476,064 Ritz et al. July 12, 1949 2,479,450 Young et al. 1 Aug. 16, 1949 2,497,458 'Kurtz, Jr. Feb. 14, 1950 2,583,420 Garberet a1 vJan. 22, 1952 FOREIGN PATENTS Number Country Date 106,371 Australia Jan. 26, 1939 516,931 Great Britain 1- Jan. 16, 1940 

1. A PROCESS FOR THE PREPARATION OF A RESINOUS POLYMER WHICH COMPRISES MIXING BUTADIENE, ISOBUTYLENE AND TOLUENE IN A RATIO OF 60/20/20, DILUTING THE MIXTURE WITH METHYL CHLORIDE, COOLING THE DILUTED SOLUTION TO A TEMPERATURE BETWEEN 0* C. AND -40* C., ADDING THERETO 10% BY WEIGHT BASED ON THE FEED OF ALUMINUM CHLORIDE CATALYST DISSOLVED IN ETHYL CHLORIDE IN A CONCENTRATION BETWEEN 0.1 AND 5% AND SEPARATING THE RESULTING RESIN FROM THE REACTION MIXTURE. 